A Luminescent 1D Silver Polymer Containing [2.2]Paracyclophane Ligands

Abstract

[2.2]Paracyclophane scaffolds have seen limited use as building blocks in supramolecular chemistry. Here, we report the synthesis and characterization of a 1D coordination polymer consisting of silver(I) ions bound to a [2.2]paracyclophane scaffold functionalized with two 4-pyridyl units. The structure of the polymer has been determined from single crystal X-ray diffraction analysis and reveals two different silver coordination motifs that alternate along the 1D coordination polymer. The coordination polymer exhibits strong blue and sky-blue fluorescence in solution and in the crystalline solid state, respectively.

[2.2]Paracyclophane Derivatives as Building Blocks for Coordination Polymers

“…= 2954 (aliphatic C-H stretching), 1717 (C=O stretching), 1605 (C=C stretching), 1434 (aliphatic C-H bending), 1270 (C-O stretching), 1101 (C-O stretching), 1016, 958, 857 (aromatic C-H bending), 765 (aromatic C-H bending), 720 (aromatic C-H bending), 466. EI-MS m/z (%): 744 (M + , 2), 444 (16), 372 (15), 339 (60), 281 (63), 253 (100), 178 (80).…”

“…Although widely used as ligands in catalytic systems, [2.2]paracyclophane derivatives have seen only limited use in metal-organic framework (MOF) design, with the few exceptions focusing mainly on the metals zirconium [10,11], silver [12][13][14][15], cobalt [16] and copper [17].…”

Room-temperature synthesis of nanometric and luminescent silver-MOFs

“…Several Ag-coordinated polymers have shown luminescence capabilities, some of them reported years ago (Ding et al, 2005); however, their emissive behavior is not well understood, with some cases showing ligand-to-metal energy transfer (through bonds) and others showing antenna effects (through space). Moreover, their emissive contributions "turn on" or vary due to particular structural arrangements between ligands, for e.g., carboxylate coordination modes, toward the Ag centers, and the number of Ag atoms in the coordinating net, but also due to the number and positions of carboxylate moieties in the linker, with emissive examples of two, three, four, or even six carboxylate moieties in the ligand (Sun et al, 2014;Xia et al, 2018;Gutiérrez et al, 2020;Yu et al, 2020;Chen et al, 2021;Mackenzie et al, 2021).…”

Silver(i) coordination polymers of trans-5-styrylpyrimidine – from structural diversity to solid-state reactivity under sunlight

“…1 Such compounds offer wide scope for studying intriguing structural diversity, 2 and various material applications ranging from gas storage and separation, 3 catalysis, 4 drug delivery, 5 sensing, 6 etc. Moreover, a wide range of physical properties, such as luminescence, 7 magnetism, 8 conductivity, 9 etc. , can be explored in such materials.…”